Agents and method for producing semi-permanent colorations of keratin fibers

ABSTRACT

The object of the present invention is a colorant for the semi-permanent tinting of keratin fibers, said colorant being based on a combination of nonoxidative dyes and polymethine dyes of the tautomeric formula (Ia)/(Ib)                    
     and a method for tinting keratin fibers.

The present invention relates to nonoxidative colorants for keratinfibers, for example hair or wool, based on a combination of natural orsynthetic nonoxidative dyes (known as “direct dyes”) and polymethinedyes, as well as to a method for coloring keratin fibers.

The coloring of hair is currently subject to the most varied trends.Whereas in the past hair was colored primarily to cover gray areas,today there is an increasing demand for integrating the hair color intocurrent fashion as an expression of personality.

Now as before, two established methods of hair coloring are available.One of these is the oxidative hair coloring which results in verydurable tints. The other method consists of the possibility of coloringhair with colorants containing nonoxidative, direct dyes (often referredto as toners). Although the dyes used for this purpose are optimized fordyeing performance as well as for remaining on the hair as long aspossible, the color shade gradually weakens with every hair washing.Thus, as a rule and depending on the product used and the type of hair,such colorants do not last more than a maximum of 10 hair washings.

Hence, a need exists for nonoxidative colorants which besides goodcoloring properties have improved color stability, particularly in termsof wash-out resistance.

Surprisingly, we have now found that colorants based on a combination ofnatural or synthetic nonoxidative dyes and polymethine dyes (in thefollowing also referred to as “oxonol dyes”) produce an outstanding and,in particular, very long-lasting coloring of keratin fibers.

Oxonol dyes have been known for a long time, and a wide range ofsubstitution patterns can be found in the literature. A review of thesedyes can be found, for example, in Houben-Weyl 5/1d, 4th edition (1954),page 227 ff. Some of these oxonol dyes are also available commercially.

By means of the colorants of the invention, it is possible to achievecolor shades of a modified natural tone, but particularly those in thefashionable range. Moreover, besides the said color shades, it ispossible to obtain a number of vivid color highlights, particularly inthe bright-red to blue range. As a result of the high tinting power ofthe dyes and their high substantivity, the original fiber color can becovered very effectively. As a result, it is possible to satisfy theaforementioned desire to integrate the hair color into fashion and toprovide an expression of personality.

The object of the present application is therefore a colorant forkeratin fibers, for example furs, feathers, wool and hair, particularlyhuman hair, characterized in that it contains a combination of (a) atleast one natural or synthetic nonoxidative dye and (b) at least onepolymethine dye having the tautomeric formula (Ia)(Ib) or aphysiologically tolerated salt thereof

wherein in general formula (Ia)(Ib) X and Y independently of each otherand together with the two carbon atoms of the ring system indicated informula (Ia)(Ib) represent the elements needed for the formation of afive-membered or six-membered heterocyclic ring, and L stands for alinking group of general formula

wherein R denotes a hydrogen atom, a phenyl, methyl or carboxamido groupor a halogen atom, and indices m and n are equal to 0, 1 or 2, the sumof m and not exceeding 2.

For example, the five-membered or six-membered heterocyclic ring ingeneral formula (Ia)(Ib) can be a pyrazolone, pyridone, isoxazolone,dioxothiazoline, rhodanine, dioxoimidazolidine, barbituric acid orthiobarbituric acid group, the two ring systems present in generalformula (Ia)(Ib) being equal or different. Preferably, taking intoaccount their tautomeric forms, these two ring systems are identical,and L stands for a monomethine, trimethine or pentamethine unit.

Suitable physiologically tolerated salts of the compounds of formula(Ia)(Ib) are, in particular, the alkali metal and ammonium salts, forexample the ammonium, triethylammonium, sodium, potassium,N-methylmorpholinium, monoethanolammonium, diethanolammonium andtriethanolammonium salts among which the sodium, potassium andparticularly the ammonium salts are preferred.

Written in their acid form, the dyes of formula (I) used in the colorantof the invention contain polymethine dyes of general formulas (II) to(IV), presented in their possible tautomeric forms

wherein R1, R1′ and R6 denote hydrogen, a straight-chain or branched C1to C8 alkyl, hydroxyethyl, dihydroxypropyl, methoxyethyl, carboxyethylor C1 to C4 sulfoalkyl group, a phenyl radical, a phenyl radicalsubstituted with one or more halogen atoms, a phenyl radical substitutedwith one or two sulfonic acid groups, a phenyl radical substituted withone or two carboxylic acid groups, a phenyl radical substituted with oneor more unbranched or branched C1 to C8 alkyl groups or C1 to C8 alkoxygroups, a benzyl radical, a benzyl radical substituted with one or morehalogen atoms, a benzyl radical substituted with a C1 to C4 alkyl, ahydroxyl, methoxy, carboxyl, nitro or amino group or a five-membered orsix-membered saturated or unsaturated heterocyclic ring, R1 and R1′being equal or different;

R2, R2′ and R7 denote hydrogen, a branched or unbranched C1 to C6 alkylgroup, a phenyl radical, an amino group which can also be acylated orsulfonylated, an acetyl or methoxy or a carboxylic acid group esterifiedwith a straight-chain or branched C1 to C8 alcohol or ethylene glycolmonomethyl ether or ethylene glycol monoethyl ether, or a carboxamido,carboxanilido or 2-amino-2-oxyethyl or nitrile group, R2 and R2′ beingequal or different; and

R3, R3′ and R8 denote hydrogen, a straight-chain or branched C1 to C11alkyl group, a monohydroxyalkyl group, a straight-chain or branched C1to C11 dihydroxyalkyl group, a straight-chain or branched C1 to C11alkoxyalkyl group, a straight-chain or branched C1 to C11 monoalkylaminogroup, an amino group having formula (CH2)_(x)—NR11R12 (wherein x standsfor an integer from 0 to 3 and R11 and R12 independently of each otherdenote a C1 to C3 alkyl group), a C2 to C4 sulfoalkyl or carboxyalkylgroup, a phenyl group or a phenyl group substituted with one or morehalogen atoms, or a phenyl group substituted with one or two sulfonicacid groups, or with one or two carboxyl groups, or with one or moreunbranched or branched C1 to C8 alkyl groups or with C1 to C8 alkoxygroups, or a benzyl group or a benzyl group substituted with one or morehalogen atoms, or with a C1 to C4 alkyl, hydroxyl, methoxy, nitro oramino group, or a phenylethyl group, a five-membered or six-memberedaromatic or nonaromatic heterocyclic ring which can be linked directlythrough a methylene group, a pyrolidino, morpholino, piperazino,piperidino or pyridino (C2 or C3) alkyl group or a trialkylammoniumgroup of formula R13—N(R14)₃ ⁺ (wherein R13 denotes a C1 to C6 alkylenegroup and R14 denotes a methyl or ethyl group, the total number ofcarbon atoms in the molecule being 5 to 9), R3 and R3′ being equal ordifferent, and

R4, R4′ and R9 denote hydrogen, a nitrile, carboxylate ester,carboxamido, sulfonic acid, sulfomethyl or methanesulfonyl group or apyridinium or imidazolium radical, R4 and R4′ being equal or different,and

R5, R5′ and R10 denote hydrogen or a C1 to C4 alkyl group or a C5-C6cycloalkyl, phenylethyl, methoxyphenyl, benzyl, phenyl or carboxylgroup, R5 and R5′ being equal or different, and

Z denotes oxygen or a radical of formula C(CN)₂, C(CN)COOQ or C(COOQ)₂wherein Q denotes a C1 to C8 alkyl group or an ethylene glycol mono-(C3to C7)-alkyl ether, and L denotes a linking group of general formula

 wherein R denotes a hydrogen atom, a phenyl, methyl or carboxamidogroup or a halogen atom, and the indices m and n equal 0, 1 or 2, thesum of m and n not exceeding 2.

Particularly preferred are dyes of general formulas (II) to (IV) and thesalts thereof wherein

R1 and R1′ are equal and denote hydrogen, a straight-chain or branchedC1 to C4 alkyl group, a hydroxyethyl, dihydroxypropyl, methoxyethyl orC2 to C4 sulfoalkyl group, a phenyl radical or a phenyl radicalsubstituted with one or more halogen atoms, one or two sulfonic acidgroups, a methyl or methoxy group, or a benzyl radical or a benzylradical substituted with a halogen atom, a methyl, hydroxyl, methoxy,nitro or amino group, and

R2 and R2′ are equal and denote a methyl group or an amino group whichcan also be acylated, or a carboxyl group possibly esterified with a C1to C3 alcohol, and R3 and R3′ are equal or different and denotehydrogen, a straight-chain C1 to C4 alkyl group, a hydroxyethyl,methoxyethyl, methoxypropyl or sulfoethyl group or a phenyl radical or aphenyl radical substituted with a halogen atom, a sulfonic acid ormethyl or methoxy group, or a benzyl radical or a benzyl radicalsubstituted with a halogen atom, a methyl, hydroxyl, methoxy, nitro oramino group or a five-membered or six-membered aromatic or nonaromaticheterocyclic ring which can be linked directly or through a methylenegroup; an amino group, a C1 to C4 monoalkylamino group or a dialkylaminogroup with a total of 2 to 8 carbon atoms in the molecule, or atrialkylammoniumalkyl group of formula R13—N(R14)₃ ⁺ (wherein R13denotes a C1 to C6 alkylene group and R14 denotes a methyl or ethylgroup, the total number of carbon atoms in the molecule being equal to 5to 9), and

R4 and R4′ are equal and denote hydrogen, a nitrile, carboxamido,sulfonic acid, sulfomethyl, methanesulfonyl, pyridinium, or imidazoliumgroup, and

R5 and R5′ are equal and denote hydrogen, a methyl or nitrile group or asubstituted or unsubstituted phenyl radical, and

R6 denotes hydrogen, a straight-chain or branched C1 to C4 alkyl groupor a hydroxyethyl, dihydroxypropyl, methoxyethyl or C2 to C4 sulfoalkylgroup or a phenyl radical or a phenyl radical substituted with one ormore halogen atoms, one or two sulfonic acid groups, a methyl or methoxygroup; a benzyl radical or a benzyl radical substituted with a halogenatom, or a methyl, hydroxyl, methoxy, nitro or amino group, and

R7 denotes a methyl group or an amino group which can also be acylated,a carboxyl group or a carboxyl group esterified with a C1 to C3 alcohol,and

R8 denotes hydrogen, a straight-chain C1 to C4 alkyl group, ahydroxyethyl, methoxyethyl or sulfoethyl group, a phenyl radical or aphenyl radical substituted with a halogen atom, sulfonic acid, methyl ormethoxy group; a benzyl radical or a benzyl radical substituted with ahalogen atom or a methyl, hydroxyl, methoxy, nitro or amino group; or afive-membered or six-membered aromatic or nonaromatic heterocyclic ringlinked directly or through a methylene group, an amino or C1 to C4monoalkylamino group, a dialkylamino group with a total of 2 to 8 carbonatoms in the molecule or a trialkylammoniumalkyl group R13—N(R14)₃ ⁺(wherein R13 denotes a C1 to C6 alkylene group and R14 denotes a methylor ethyl group, the total number of carbon atoms in the molecule being 5to 9), and

R9 denotes hydrogen, a nitrile, carboxamido, sulfonic acid, sulfomethyl,pyridinium or imidazolium group, and

R10 denotes hydrogen, a methyl or nitrile group or a substituted orunsubstituted phenyl radical, and

Z denotes oxygen or a C(CN)₂ group, and

L is a linking group of general formula

 wherein R stands for a hydrogen atom or a methyl group, and the indicesm and n are equal to 0, 1 or 2, the sum of m and n not exceeding 2.

The compounds shown in the following (in one of their possibletautomeric forms) are examples of the aforesaid preferred dyes offormulas (II) to (IV). Written in their acid form, they are as follows.

4-(5-Hydroxy-1,3-dimethyl-1H-pyrazol-4-ylmethylen)-2,5-dimethyl-2,4-dihydropyrazol-3-one(1)

2-(2-Hydroxyethyl)4-(5-hydroxy-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-4-ylmethylen)-5-methyl-2,4-dihydropyrazol-3-one(2)

4-(5-Hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-ylmethylen)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one(3)

4-(3-(5-Hydroxy-1,3-dimethyl-1H-pyrazol4-yl)-allyliden)-2,5-dimethyl-2,4-dihydropyrazol-3-one(4)

5-Amino-4-(3-(3-amino-5-hydroxy-1-phenyl-1H-pyrazol-4-yl)-allyliden)-2-phenyl-2,4-dihydropyrazol-3-one(5)

2-(2-Hydroxyethyl)-4-(3-(5-hydroxy-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-4-yl)-allyliden)-5-methyl-2,4-dihydro-pyrazol-3-one(6)

4-(3-(5-Hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-allyliden)-5-methyl-2-(4-sulfophenyl)-2,4-dihydro-pyrazol-3-one(7)

4-(3-(5-Hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-but-2-enyliden)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one(8)

4-(3-(3-Carboxy-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-yliden)-propenyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylicacid (9)

5-Hydroxy4-(3-(3-methoxycarbonyl-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-yliden)-propenyl)-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylicacid methyl ester (10)

4-(5-(5-Hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)-penta-2,4-dienyliden)-2,5-dimethyl-2,4-dihydropyrazol-3-one(11)

5-Amino-4-(5-(3-amino-5-hydroxy-1-phenyl-1H-pyrazol-4-yl)-penta-2,4-dienyliden)-2-phenyl-2,4-dihydropyrazol-3-one(12)

2-(2-Hydroxyethyl)-4-(5-(5-hydroxy-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-4-yl)-penta-2,4-dienyliden)-5-methyl-2,4-dihydro-pyrazol-3-one(13)

4-(5-(5-Hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-penta-2,4-dienyliden)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one(14)

4-(5-(3-Carboxy-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-yliden)-penta-1,3-dienyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylicacid (15)

6-Hydroxy-1-(2-hydroxyethyl)-5-(3-(1-(2-hydroxyethyl)-3-methyl-5-oxo-1,5-dihydro-pyrazol-4-yliden)-propenyl)-4-methyl-2-oxo-1,2-dihydro-pyridin-3-carbonitrile(16)

6-Hydroxy-5-(3-(1-(2-hydroxyethyl)-3-methyl-5-oxo-1,5-dihydro-pyrazol-4-yliden)-propenyl)-4-methyl-2-oxo-1-(4-sulfophenyl)-1,2-dihydro-pyridin-3-carbonitrile(17)

6-Hydroxy-4-methyl-5-(3-(3-methyl-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-yliden)-propenyl)-2-oxo-1-(4-sulfophenyl)-1,2-dihydropyridin-3-carbonitrile(18)

6-Hydroxy-4-methyl-5-(3-(3-methyl-5-oxo-1-phenyl-1,5-dihydropyrazol-4-yliden)-propenyl)-2-oxo-1-(3-sulfophenyl)-1,2-dihydropyridin-3-carbonitrile(19)

4-(3-(5-Cyano-2-hydroxy4-methyl-6-oxo-1-phenyl-1,6-dihydropyridin-3-yl)-allyliden)-5-oxo-1-(4-sulfophenyl)-4,5-dihydro-1H-pyrazol-3-carboxylicacid (20)

6-Hydroxy-5-(3-(1-(2-hydroxyethyl)-3-methyl-5-oxo-1,5-dihydropyrazol-4-yliden)-propenyl)-4-methyl-2-oxo-1-phenyl-1,2-dihydropyridin-3-carbonitrile(21)

5-(3-(4-Carboxy-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-2-oxo-1,2-dihydropyridin-4carboxylicacid (22)

2-(3-Cyano-5-(3-(5-cyano-6-dicyanomethylen-4-methyl-2-oxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-4-methyl-1H-pyridin-2-yliden)-malononitrile(23)

5-(3-(5-Cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridin-3-carbonitrile (24)

5-(3-(5-Cyano-1-(2-hydroxyethyl)-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-1-(2-hydroxyethyl)-4-methyl-2-oxo-1,2-dihydropyridin-3-carbonitrile(25)

5-(3-(5-Cyano-1-ethyl-4-(4-methoxyphenyl)-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-ethyl-6-hydroxy-4-(4-methoxyphenyl)-2-oxo-1,2-dihydropyridin-3-carbonitrile(26)

1-Butyl-5-(3-(1-butyl-5-cyano-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridin-3-carbonitrile(27)

5-(3-(5-Cyano-1-(3-methoxy-propyl)4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-1-(3-methoxy-propyl)-4-methyl-2-oxo-1,2-dihydropyridin-3-carbonitrile(28)

5-(3-(5-Cyano-1-cyclohexyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridin-3-carbonitrile(29)

5-(3-(5-Cyano-4-methyl-1-(2-morpholin-4-yl-ethyl)-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-4-methyl-1-(2-morpholin-4-yl-ethyl)-2-oxo-1,2-dihydropyridin-3-carbonitrile(30)

5-(3-(5-Cyano-4-methyl-2,6-dioxo-1-(4-sulfophenyl)-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-4-methyl-2-oxo-1-(4-sulfophenyl)-1,2-dihydropyridin-3-carbonitrile(31)

5-(3-(5-Cyano-4-methyl-2,6-dioxo-1-(3-sulfophenyl)-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-6-hydroxy-4-methyl-2-oxo-1-(3-sulfophenyl)-1,2-dihydropyridin-3-carbonitrile(32)

5-(3-(5-Cyano-1-dimethylamino-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-dimethylamino-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridin-3-carbonitrile(33)

5-(3-(5-Carbamoyl-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridin-3-carboxamide(34)

1-Ethyl-3-(3-(1-ethyl-2-hydroxy-5-methansulfonyl-4-methyl-6-oxo-1,6-dihydro-pyridin-3-yl)-allyliden)-5-methansulfonyl-4-methyl-3H-pyridin-2,6-dione(35)

5-(5-(5-Cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-penta-1,3-dienyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridin-3-carbonitrile(36)

Preferred among the aforesaid dyes are, in particular the compounds offormula (II) to (IV) wherein

R1 and R1′ are equal and denote a phenyl, sulfophenyl, methyl orhydroxyethyl group,

R2 and R2′ are equal and denote hydrogen, a methyl, carboxyl,carboxylate ester or amino group,

R3 and R3′ independently of each other denote hydrogen or astraight-chain C1 to C4 alkyl group, a methoxy, hydroxyethyl,sulfoethyl, phenyl or sulfophenyl group,

R4 and R4′ are equal and denote hydrogen, or a nitrile or carboxamidogroup,

R6 denotes a phenyl, sulfophenyl, methyl or hydroxyethyl group,

R7 denotes hydrogen, or a methyl, carboxyl, carboxylate ester or aminogroup,

R8 denotes hydrogen or a straight-chain C1 to C4 alkyl group, amethoxyethyl, hydroxyethyl, sulfoethyl, phenyl or sulfophenyl group,

R9 denotes a nitrile group,

R10 denotes a methyl or carboxyl group,

Z denotes oxygen,

R denotes a hydrogen atom or a methyl group, and the indices m and nequal 0, 1 or 2, the sum of m and n having a maximum value of 2.

In the case of dyes with a pronounced anionogenic character (this istrue primarily for dyes containing acid functions such as sulfonic acidor carboxyl groups), the dyes can be used also in the form of theirphysiologically tolerated salts. Suitable, in particular, are thefollowing compounds.

Diammonium-4-(5-hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl-methylen)-5-methyl-2-(4-sulfophenyl)-2,4-dihydro-pyrazol-3-one(3a)

Disodium4-(3-(5-hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-allyliden)-5-methyl-2-(4-sulfophenyl)-2,4-dihydro-pyrazol-3-one(7a)

Tripotassium4-(3-(5-hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-but-2-enyliden)-5-methyl-2-(4-sulfophenyl)-2,4-dihydro-pyrazol-3-one(8a)

Tetrasodium4-(3-(3-Carboxy-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-yliden)-propenyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylicacid (9a)

Dipotassium4-(5-(5-Hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-penta-2,4-dienyliden)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one(14a)

Dipotassium4-(5-(3-carboxy-5-oxo-1-(4-sulfo-phenyl)-1,5-dihydro-pyrazol-4-yliden)-penta-1,3-dienyl)-5-hydroxy-1-(4-sulfo-phenyl)-1H-pyrazol-3-carboxylicacid (15a)

Triethylammonium-5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydro-pyridin-3-carbonitrile(24a)

Ammonium5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-yliden)-propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydro-pyridin-3-carbonitrile(24b)

The total amount of dyes of formula (Ia)(Ib) or (II) to (IV) in thecolorants according to the invention for coloring keratin dyes is from0.01 to 5 wt % and preferably from 0.5 to 4 wt %.

The colorants according to the invention also contain at least onenatural or synthetic nonoxidative dye. Suitable synthetic nonoxidativedyes are, for example, the nitro, azo, triphenylmethane, quinone,anthraquinone or acid dyes, particularly

1,4-bis-[(2-hydroxyethyl)amino]-2-nitrobenzene,1-(2-hydroxyethyl)amino-2-nitro-4-[di(2-hydroxyethyl)amino]benzene (HCBlue No. 2), 1-amino-3-methyl-4-[(hydroxyethyl)amino-6-nitrobenzene (HCViolet No. 1),4-[ethyl-(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzenehydrochloride (HC Blue No. 12),4-[di(2-hydroxyethyl)amino]-1-[(2-methoxyethyl)amino-2-nitrobenzene (HCBlue No. 11),1-[2,3-dihydroxypropyl)amino-4-[methyl-2-(2-hydroxyethyl)amino]-2-nitrobenzene(HC Blue No. 10),1-[(2,3-dihydroxypropyl)amino]-4-[ethyl-(2-hydroxyethyl)amino]-2-nitrobenzenehydrochloride (HC Blue No. 9),1-(3-hydroxypropylamino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene (HCViolet No. 2),1-methylamino-4-[methyl-(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HCBlue No. 6), 2-[(4-amino-2-nitrophenyl)amino]-5-dimethylaminobenzoicacid (HC Blue No. 13), 1-amino-4-[(2-hydroxyethyl)amino]-2-nitrobenzene(HC Red No. 7), 2-amino-4,6-dinitrophenol, 4-amino-2-nitrodiphenylamine(HC Red No. 1), 1-amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzenehydrochloride (HC Red No. 13),1-amino-5-chloro-4-[(2-hydroxyethyl)amino]-2-nitrobenzene,4-amino-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 3),4-amino-3-nitrophenol, 4-[(2-hydroxyethyl)amino-3-nitrophenol,1-[(2-aminoethyl)amino]-4-(2-hydroxyethoxy)-2-nitrobenzene (HC OrangeNo. 2),4-(2,3-dihydroxypropoxy)-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HCOrange No. 3),1-amino-5-chloro-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC RedNo. 10), 5-chloro-1,4-[di(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HCRed No. 11), 2-[(2-hydroxyethyl)amino]-4,6-dinitrophenol,4-ethylamino-3-nitrobenzoic acid,2-[(4-amino-2-nitrophenyl)amino]benzoic acid,2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitrophenolhydrochloride, 4-[(3-hydroxypropyl)amino]-3-nitrophenol,2,5-diamino-6-nitropyridine, 1,2,3,4-tetrahydro-6-nitroquinoxaline,7-amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red No. 14),1-amino-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 5),1-(2-hydroxyethoxy)-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC YellowNo. 4), 1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Yellow No. 2),2-[(hydroxyethyl)amino]-1-methoxy-5-nitrobenzene, 2-amino-3-nitrophenol,1-(2-hydroxyethoxy)-3-methylamino-4-nitrobenzene,2,3-(dihydroxpropoxy)-3-methylamino-4-nitrobenzene,2-[(2-hydroxyethyl)amino]-5-nitrophenol (HC Yellow No. 11),3-[(2-aminoethyl)amino]-1-methoxy-4-nitrobenzene hydrochloride (HCYellow No. 9), 1-[(2-ureidoethyl)amino]-4-nitrobenzene,4-[(2,3-dihydroxypropyl)amino]-3-nitro-1-trifluoromethylbenzene (HCYellow No. 6), 1-chloro-2,4-bis-[(2-hydroxyethyl)amino]-5-nitrobenzene(HC Yellow No. 10), 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene,1-chloro-4-[(2-hydroxyethyl)-amino-3-nitrobenzene (HC Yellow No. 12),4-[(2-hydroxyethyl)amino-3-nitro-1-trifluoromethylbenzene (HC Yellow No.13), 4-[(2-hydroxyethyl)amino]-3-nitrobenzonitrile (HC Yellow No. 14),4-[(2-hydroxyethyl)amino]-3-nitrobenzamide (HC Yellow No. 15,1,4-di[(2,3-dihydroxypropyl)amino]-9,10-anthraquinone,1-[(2-hydroxyethyl)amino]-4-methylamino-9,10-anthraquinone (C.I. 61505,Disperse Blue No. 3), 2-[(2-aminoethyl)amino]-9,10-anthraquinone (HCOrange No. 5),1-hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthraquinone,1-[(3-aminopropyl)amino]-4-methylamino-9,10-anthraquinone (HC Blue No.8), 1-[(3-aminopropyl)amino]-9,10-anthraquinone (HC Red No. 8),1,4-diamino-2-methoxy-9,10-anthraquinone (C.I. 62015, Disperse Red No.11, Solvent Violet No. 26),1,4-dihydroxy-5,8-bis-[(2-hydroxyethyl)amino]-9,10-anthraquinone (C.I.62500, Disperse Blue No. 7, Solvent Blue No. 69),1-[(di(2-hydroxyethyl)amino]-3-methyl-4-[(4-nitrophenyl)azo]benzene(C.I. 11210, Disperse Red No. 17),4-[(4-aminophenyl)azo]-1-[di(2-hydroxyethyl)amino]-3-methylbenzene (HCYellow No. 7), 2,6-diamino-3-[(pyridin-3-yl)azo)pyridine,6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonic acid disodiumsalt (C.I. 15985; Food Yellow No. 3; FD&C Yellow No. 6),2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt (C.I. 10316; AcidYellow No. 1); Food Yellow No. 1),2-(indan-1,3-dione-2-yl)quinoline-x,x-sulfonic acid (mixture of mono anddisulfonic acid) (C.I. 47005; D&C Yellow No. 5; Food Yellow No. 13);Acid Yellow No. 3),5-hydroxy-1-(4-sulfophenyl)-[(4-[(4-sulfophenyl)azo]pyrazole-3-carboxylicacid trisodium salt (C.I. 19140; Food Yellow No. 4; Acid Yellow No. 23),9-(2-carboxyphenyl)-6-hydroxy-3H-xanthen-3-one (C.I. 45350; Acid YellowNo. 73; D&C Yellow No. 8),5-[(2,4-dinitrophenyl)amino]-2-phenylaminobenzenesulfonic acid sodiumsalt (C.I. 10385; Acid Orange No. 3),4-[(2,4-dihydroxyphenyl)axo]benzenesulfonic acid monosodium salt (C.I.14270; Acid Orange No. 6), 4-[(2-hydroxy-1-naphthyl)azo)benzenesulfonicacid sodium salt (C.I. 15510; Acid Orange No. 7),4-[(2,4-dihydroxy-3-[(2,4-dimethylphenyl)azo]phenyl)azo]benzenesulfonicacid sodium salt (C.I. 20170; Acid Orange No. 24),4-hydroxy-3-[(4-sulfo-1-naphthyl)azo]-1-naphthalenesulfonic aciddisodium salt (C.I. 14720; Acid Red No. 14),6-hydroxy-5-[(4-sulfo-1-naphthyl)azo-2,4-naphthalenedisulfonic acidtrisodium salt (C.I. 16255; Ponceau 4R; Acid Red No. 18),3-hydroxy-4-[(4-sulfo-1-naphthyl)azo]-2,7-naphthalenedisulfonic acidtrisodium salt (C.I. 16185; Acid Red No. 27),8-amino-1-hydroxy-2-(phenylaxo)-3,6-naphthalenedisulfonic acid disodiumsalt (C.I. 17200; Acid Red No. 33),5-(acetylamino)-4-hydroxy-3-[(2-methylphenyl)azo]-2,7-naphthalenedisulfonicacid disodium salt (C.I. 18065; Acid Red No.35),2-(3-hydroxy-2,4,5,7-tetraiododibenzopyran-6-one-9-yl)benzoic aciddisodium salt (C.I. 45430; Acid Red No. 51),N-[6-(diethylamino)-9-(2,4-disulfophenyl)-3H-xanthen-3-ylidene-N-ethylethaneammoniumhydroxide, inner salt, sodium salt (C.I. 45100; Acid Red No. 52),8-[(4-(phenyl-azo) phenyl)azo]-7-naphthol-1,3-disulfonic acid disodiumsalt (C.I. 27290; Acid Red No. 73),2′,4′,5′,7′-tetrabromo-3′,6′-dihydroxyspiro[isobenzofuran-1(3H),-9′[9H]xanthene-3-onedisodium salt (C.I. 45380; Acid Red No. 87),2′,4′,5′,7′-tetrabromo-4,5,6,7-tetrachloro-3′,6′-dihydroxyspiro[isobenzofuran 1(3H),9′[9H]xanthene]-3-one disodiumsalt (C.I. 45410; Acid Red No. 92),3′,6′-dihydroxy-4′,5′-diiodospiro[isobenzofuran-1(3H),9′(9H)-xanthene]-3-onedisodium salt (C.I. 45425; Acid Red No.95),(2-sulfophenyl)-di-[4-(ethyl((4-sulfophenyl) methyl)-amino)phenyl]carbenium disodium salt, betaine (C.I. 42090; Acid Blue No. 9;FD&C Blue No. 1),1,4-bis-[(2-sulfo-4-methylphenyl)amino]-9,10-anthraquinone disodium salt(C.I. 61570; Acid Green No. 25),bis-[4-dimethylamino)phenyl]-(3,7-disulfo-2-hydroxy-1-naphthyl)carbeniuminner salt, monosodium salt (C.I. 44090; Food Green No. 4; Acid GreenNo. 50), bis-[4-(diethylamino)phenyl]-(2,4-disulfophenyl)carbenium innersalt, sodium salt (2:1) (C.I. 42045; Food Blue No. 3; Acid Blue No. 1),bis-[4-(diethylamino)phenyl](5-hydroxy-2,4-disulfophenyl)carbenium innersalt, calcium salt (2:1) (C.I. 42051; Acid Blue No. 3),1-amino-4-(cyclohexylamino)-9,10-anthraquinone-2-sulfonic acid sodiumsalt (C.I. 62045; Acid Blue No. 62),2-(1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene)-2,3-dihydro-3-oxo-1H-indol-5-sulfonicacid disodium salt (C.I. 73015; Acid Blue No. 74),9-(2-carboxy-phenyl)-3-[(2-methylphenyl)amino]-6-[(2-methyl-4-sulfophenyl)amino]xanthyliuminner salt, monosodium salt (C.I. 45190; Acid Violet No.9),1-hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthraquinone sodiumsalt (C.I. 60730; D&C Violet No.2; Acid Violet No. 43),bis-[3-nitro-4-[(4-phenylamino)-3-sulfophenylamino]phenyl]sulfone (C.I.10410; Acid Brown No. 13),5-amino-4-hydroxy-6-[(4-nitrophenyl)azo]-3-(phenylazo)-2,7-naphthalenedisulfonicacid disodium salt (C.I. 20470; Acid Black No. 1),3-hydroxy-4-[(2-hydroxy-1-naphthyl)azo-7-nitro-1-naphthalenesulfonicacid chromium complex (3:2) (C.I. 15711; Acid Black No.52),3-[(2,4-dimethyl-5-sulfophenyl)azo]-4-hydroxy-1-naphthalenesulfonic aciddisodium salt (C.I. 14700; Food Red No. 1; Ponceau SX; FD&C Red No. 4),4-(acetylamino)-5-hydroxy-6-[(7-sulfo-4-[(4-sulfophenyl)azo]-1-naphthyl)azo]-1,7-naphthalenedisulfonicacid tetrasodium salt (C.I. 28440; Food Black No.1) and3-hydroxy-4-(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-ylazo)naphthalene-1-sulfonicacid sodium salt chromium complex (Acid Red No. 195).

Although the polymethine dyes contained in the colorant according to theinvention are by definition anionic in nature, some of these dyes,particularly monomethine oxonols (1) and (2) are, surprisingly, fullycompatible with cationic (“basic”) dyes, for example9-(dimethylamino)benzo[a]phenoxazin-7-ium chloride (C.I. 51175; BasicBlue No. 6), di[4-diethylamino)phenyl][4-(ethylamino)naphthyl]-carbeniumchloride (C.I. 42595; Basic Blue No. 7),3,7-di(dimethylamino)phenothiazin-5-ium chloride, (C.I. 52015; BasicBlue No. 9),di[4-(dimethylamino)phenyl][4-(phenylamino)naphthyl]carbenium chloride(C.I. 44045); Basic Blue 26),2-[4-(ethyl(2-hydroxyethyl)amino)phenyl)axo]-6methoxyoxy-3-methylbenzothiazoliummethylsulfate (C.I. 11154; Basic Blue 41),8-amino-2-bromo-5-hydroxy-4-imino-6-[(3-(trimethylammonio)phenyl)amino]-1(4H)-naphthalenonechloride (C.I. 56059; Basic Blue No. 99),bis[4-(dimethylamino)phenyl][4-(methylamino)phenyl]carbenium chloride(C.I. 42535, Basic Violet No. 1),tris-[4-(dimethylamino)phenyl]carbenium chloride (C.I. 42555; BasicViolet No. 3), 2-[3,6-diethylamino)dibenzopyranium-9-yl benzoic acidchloride (C.I. 45170; Basic Violet No. 10),di(4-aminophenyl)-(4-amino-3-methylphenyl)carbenium chloride (C.I.42510; Basic Violet No. 14),1,3-bis[(2,4-diamino-5-methylphenyl)azo]-3-methylbenzene (C.I. 21010,Basic Brown No. 4),1-[(4-aminophenyl)azo-7-(trimethylammonio)-2-naphthol chloride (C.I.12250, Basic Brown No. 16),1-[(4-aminophenyl)azo-7-(trimethylammonio)-2-naphthol chloride (C.I.12250, Basic Brown No. 16),1-[(4-amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride(Basic Brown No.17),1-[(4-amino-3-nitrophenyl)azo]-7-(trimethylammonio)-2-naphtholchloride (C.I. 12251; Basic Brown No. 17) [sic—Translator],3,7-diamino-2,8-dimethyl-5-phenylphenazinium chloride (C.I. 50240; BasicRed No. 2),1,4-dimethyl-5-[(4-(dimethylamino)phenyl)azo]-1,2,4-triazolium chloride(C.I. 11055; Basic Red No. 22),2-hydroxy-1[(2-methoxyphenyl)azo-7-(trimethylammonio)naphthalenechloride (C.I. 12245; Basic Red No. 76),2-[2-(2,4-dimethoxyphenyl)amino)ethenyl]-1,3,3-trimethyl-3H-indol-1-iumchloride (C.I. 48055; Basic Yellow No. 11),3-methyl-1-phenyl-4-[(3-(trimethylammonio)phenyl)azo]pyrazol-5-onechloride (C.I. 12719; Basic Yellow No. 57) orbis-[4-(diethylamino)phenyl]phenylcarbenium hydrogen sulfate (1:1) (C.I.42040; Basic Green No: 1).

The total amount of natural or synthetic nonoxidative dyes contained inthe colorant according to the invention is from 0.01 to 15 wt % andparticularly from 0.1 to 12 wt %.

To increase the color intensity, conventional carriers used in cosmeticsystems can be employed. Suitable compounds are, for example, benzylalcohol, furfuryl alcohol, 2-hydroxymethylthiophene, vanillin orisovanillin. Other suitable carriers are described in German UnexaminedPatent Application DE 196 18 595, the disclosures of which are herebyincorporated by reference.

The colorants according to the invention for tinting keratin fibers canbe used in the form of, for example, a solution, particularly anaqueous-alcoholic solution, or a cream, gel or emulsion. Suitablesolvents besides water are, for example the lower aliphatic monohydricor polyhydric alcohols, the esters and ethers thereof or mixtures ofsaid solvents with each other or with water. The maximum boiling pointof the aforesaid suitable solvents is about 400° C., a boiling pointfrom 20° C. to 250° C. being preferred.

It is also possible to dispense said colorants by means of an atomizeror some other suitable pumping or spraying device or, in admixture withconventional propellants liquefied under pressure, dispense them from apressurized container in the form of an aerosol spray or aerosol foam.

The pH of the colorants according to the invention is from 2 to 11, a pHfrom 2.5 to 8 being particularly preferred. An alkaline pH is preferablyobtained with ammonia, but an organic amine, for examplemonoethanolamine or triethanolamine, can be used in place of ammonia. Toobtain an acidic pH, on the other hand, an organic or inorganic acid,for example hydrochloric, sulfuric, phosphoric, ascorbic, glycolic orlactic acid, can be used.

Naturally, the aforedescribed colorants can optionally contain othercommon additives suitable for keratin fiber colorants, for examplehair-care agents, wetting agents, thickeners, softeners, preservativesand perfumes as well as other additives listed in the following.

The colorants according to the invention can also contain wetting agentsor emulsifiers from the classes of anionic, amphoteric, nonionic orzwitterionic surface-active agents, such as fatty alcohol sulfates,alkanesulfonates, alkylbenzenesulfonates, alkylbetaines,α-olefinsulfonates, ethoxylated fatty alcohols, ethoxylatednonylphenols, fatty alkanolamines, ethoxylated fatty esters, fattyalcohol polyglycol ether sulfates, alkyl polyglucosides, thickeners suchas the higher fatty alcohols, starch, alginates, bentonites, cellulosederivatives, vaseline, paraffin oil and fatty acids, water-solublepolymeric thickeners such as various types of natural gum, guar gum,xanthan gum, carob bean flour, pectin, dextran, agar, amylose,amylopectin, dextrins, clays, or fully synthetic hydrocolloids, such aspolyvinyl alcohol, furthermore hair-care agents such as lanolinderivatives, cholesterol, pantothenic acid, water-soluble polymers,protein derivatives, provitamins, vitamins, plant extracts, sugar andbetaine, auxiliary agents such as humectants, electrolytes,antioxidants, fatty amides, sequestrants, film-forming agents andpreservatives.

The aforedescribed colorants can also contain natural or syntheticpolymers or modified natural polymers whereby the keratin fiber isstrengthened while it is being colored. Such agents are generallyreferred to as shade or color enhancers. Suitable among the syntheticpolymers known to be used in cosmetics for this purpose are, forexample, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, orpolyacrylic compounds, such as polyacrylic acid or polymethacrylic acid,polyacrylonitrile, polyvinyl acetates and copolymers of such compounds,for example polyvinylpyrrolidone-vinyl acetate copolymers. Suitablenatural or modified natural polymers are, for example, chitosan,(deacetylated chitin) or chitosan derivatives.

The said constituents are used in amounts that are normal for suchpurposes. For example, the wetting agents and emulsifiers are used in anamount of about 0.5 to 30 wt %, the thickeners in an amount from about0.1 to 25 wt % and the hair-care agents in an amount from about 0.1 to 5wt %. The aforesaid polymers can be used in the colorants of theinvention in amounts that are normal for such colorants, particularly inan amount from about 1 to 5 wt %.

The keratin fiber colorants of the invention are particularly wellsuited for the coloring of hair. For this purpose, the colorants of theinvention are applied to the hair in the usual manner in an amountsufficient for hair coloring and, in general, in an amount from about 50to 150 grams. After an exposure time sufficient for hair coloring,usually about 10 to 45 min at 20° to 50° C. and preferably 15 to 30 minat about 40° C., the hair is rinsed with water, optionally washed with ashampoo and/or an aqueous solution of a weak organic acid, for examplecitric or tartaric acid, again rinsed and then dried.

The colorants with the additional strengthening action are used in theknown and conventional manner by wetting the hair with them, styling thehair and then drying.

As regards the range of possible coloring, the hair colorants accordingto the invention can give rise to a broad spectrum of different shadesranging from natural colors to highly fashionable bright shades,depending on the type and composition of the dyes used. The advantageousproperties of the novel colorants manifest themselves particularly onlight-damaged and weather-damaged or permanently waved hair. Inparticular, the resulting tints are characterized by very good stabilityand wash-out resistance.

The monomethine oxonol dyes (m=n=0) can be prepared from thecorresponding heterocyclic compounds and trialkyl orthoesters orformamides as bridge precursors. Numerous compounds are described by B.Schied, J. prak. Chem 157, page 203 ff (1941) and by S. Hünig, Annalen574, page 106 ff (1951) as well in the literature cited therein.According to German Unexamined Patent Application DE 20 12 050, thetrimethine oxonols (m+n=1) can be prepared from tetramethoxypropane,trimethoxypropene or malonaldehyde dianil. The pentamethine oxonols(m+n=2) can be prepared from N-acceptor-substituted pyridinium salts byopening the pyridine ring (“Zincke cleavage”) or from an appropriatederivative, for example glutaconaldehyde dianil. A complete review ofthis subject can be found in Houben-Weyl 7/1, 4th edition (1954) onpages 263 ff and in the literature cited therein.

The following examples are intended to illustrate the object of theinvention in greater detail without limiting it to these examples.

EXAMPLES Example 1 Method for Preparing2-(2-Hydroxyethyl)-4-(5-hydroxy-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-4-ylmethylene)-5-methyl-2,4-dihydropyrazol-3-one(2)

17 g of 1-(2-hydroxyethyl)-3-methyl-1H-pyrazole and 7 g of trimethylorthoformate were allowed to reflux in 50 mL of pyridine. After 15hours, the mixture was cooled and the precipitate was filtered off.Recrystallization from 220 mL of ethanol gave 9.5 g of2-(2-hydroxyethyl)-4-(5-hydroxy-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-4-ylmethylene)-5-methyl-2,4-dihydropyrazol-3-one(2) in the form of shiny yellow needles.

Melting point: 212-214° C. λ_(max) (H₂O): 404 nm ε: 55,200 Elementalanalysis: (C₁₃H₁₈N₄O₄) C H N Calcd. 53.05% 6.16% 19.04% Found 53.04%6.15% 19.11%

Example 2 Method for Preparing Ammonium5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile(24b)

(a) 26.5 g of5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrileand 5.2 g of ammonium acetate in 250 mL of acetic acid were heated at80° C. for 2 hours. This gave a thick dye suspension. The dye suspensionwas then cooled, and the dye was filtered off and dried. This gave 25.5g of ammonium5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-1-ethyl-6hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile(24b).

Melting point: 300-301° C. λ_(max) (methanol): 596 nm ε 177,500Elemental analysis: C₂₁H₂₀N₄O₄ × NH₃ C H N Calcd. 61.50% 5.66% 17.11%Found 61.53% 5.79% 17.07%

(b) 4.9 g of commercial triethylammonium5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile(24a) was made to react with 0.8 g of ammonium acetate in 75 mL ofacetic acid as described under (a). This gave 3.6 g of dye (24a).

Example 3 Colorant

0.7 g of 2-(2-hydroxyethyl)-4-(5-hydroxy-1-(2-hydroxyethyl)- 3-methyl-1H-pyrazol-4-ylmethylene)-5-methyl-2,4- dihydropyrazol-3-one (2) 0.6 g of1-[(2-hydroxyethyl)amino]-4-methylamino-9,10- anthraquinone (C.I. 61505,Disperse Blue No. 3) 20.0 g of ethanol to 100.0 g water, demineralized

The foregoing colorant solution was applied to bleached hair. After anexposure time of 20 min at 40° C., the hair was washed with water anddried. The hair color was of a blue-green shade. After the washing test,a slight color loss, particularly of the conventional direct dye(Disperse Blue No. 3), was observed visually.

Color loss, L* a* b* ΔE_(1/2) % Untreated 84, 80  −0, 75 11, 53 hairColored hair 36, 30 −12, 60 −8, 04 53, 63 5x washed and 42, 28 −15, 09−5, 56  6, 94 13 dried hair

Example 4 Colorant

5.0 g of ethanol 1.5 g of glycolic acid 2.0 g of sodium cocoamphoacetate(50% aqueous solution) 5.0 g of benzyl alcohol 1.7 g of triethylammonium5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihy- dropyridine-3-carbonitrile(24a) 1.5 g of 6-hydroxy-5-[(4-sulfo-1-naphthyl)azo]-2,4-napthalenedisulfonic acid trisodium salt (C.I. 16255; Acid Red No. 18)to 100.0 g water, demineralized.

The foregoing colorant solution was applied to bleached hair. After anexposure time of 20 min at 40° C., the hair was washed with water anddried. The hair color was of a blue-violet shade.

After the washing test, no color loss was observed visually.

Color loss, L* a* b* ΔE_(1/2) % Untreated 84, 80 −0, 75  11, 53 hairColored hair 20, 48 18, 23 −25, 38 76, 55 5x washed and 22, 71 21, 44−27, 47  4, 43 6 dried hair

Example 5 Colorant

5.0 g of ethanol 1.5 g of glycolic acid 2.0 g of sodium cocoamphoacetate(50% aqueous solution) 5.0 g of benzyl alcohol 1.4 g of disodium4-(3-(5-hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-allylidene)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one (7a) 0.5 g of4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene to 100.0 g water,demineralized

The foregoing colorant solution was applied to bleached hair. After anexposure time of 20 min at 40° C., the hair was washed with water anddried. The hair color was of a vivid red shade. After the washing test,no color loss was observed visually.

Color loss, L* a* b* ΔE_(1/2) % Untreated 84, 80  −0, 75 11, 53 hairColored hair 39, 39 65, 56 36, 61 84, 19 5x washed and 39, 51 66, 38 37,32  1, 09 1 dried hair

Example 6 Colorant

5.0 g of ethanol 1.5 g of glycolic acid 2.0 g of sodium cocoamphoacetate(50% aqueous solution) 5.0 g of benzyl alcohol 1.8 g of dipotassium4-(5-(3-carboxy-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-ylidene)penta-1,3-dienyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazole-3-carboxylic acid (15a) 0.1 g of5-chloro-1,4-[di(2,3-dihydroxypropyl)amino]-2- nitrobenzene (HC Red No.11) to 100.0 g water, demineralized

The foregoing colorant solution was applied to bleached hair. After anexposure time of 20 min at 40° C., the hair was washed with water anddried. The hair color was of a dark egg plant shade. After the washingtest, no color loss was observed visually.

Color loss, L* a* b* ΔE_(1/2) % Untreated 84.80 −0.75 11.53 hair Coloredhair 18.43 2.83 −2.39 67.91 5x washed and 21.35 3.37 −3.87 3.32 5 driedhair

Example 7 Colorant

5.0 g of ethanol 1.5 g of glycolic acid 2.0 g of sodium cocoamphoacetate(50% aqueous solution) 5.0 g of benzyl alcohol 0.7 g of2-(2-hydroxyethyl)-4-(5-hydroxy-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-4-yl-methylene)-5-methyl-2,4- dihydropyrazol-3-one (2)0.6 g of dipotassium 4-(5-(3-carboxy-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-ylidene)penta-1,3-dienyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylic acid 0.5 g of2-amino-6-chloro-4-nitrophenol hydrochloride 100.0 g water,demineralized.

The foregoing colorant solution was applied to bleached hair. After anexposure time of 20 min at 40° C., the hair was washed with water anddried. The hair color was of a medium brown shade. After the washingtest, no color loss was observed visually.

Color loss, L* a* b* ΔE_(1/2) % Untreated 84.80 −0.75 11.53 hair Coloredhair 25.14 2.16 11.89 59.73 5× washed and 24.07 3.21 10.42 2.10 4 driedhair

Example 8 Colorant

5.0 g of ethanol 1.5 g of glycolic acid 2.0 g of sodium cocoamphoacetate(50% aqueous solution) 5.0 g of benzyl alcohol 1.2 g of5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (24a) 0.8 g of tetrasodium4-(3-(carboxy-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-ylidene)propenyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylate (9a) 0.5 g of dipotassium4-(5-3-carboxy-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-ylidene)penta-1,3-dienyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazole-3-carboxylic acid (15a) 0.7 g of5-hydroxy-1-(4-sulfophenyl)-4-[(4-sulfophenyl)azo]pyrazole- 3-carboxylicacid trisodium salt (C.I. 19140; Acid Yellow No. 23) 100.0 g water,demineralized.

The foregoing colorant solution was applied to bleached hair. After anexposure time of 20 min at 40° C., the hair was washed with water anddried. The hair color was of a greenish-blue shade. After the washingtest, hardly any color loss was observed visually.

Color loss, L* a* b* ΔE_(1/2) % Untreated 84.80 −0.75 11.53 hair Coloredhair 21.94 5.95 −11.69 67.35 5× washed and 24.63 4.68 −11.94 2.99 4dried hair

Example 9 Colorant

10.0 g of ethanol 10.0 g of sodium lauryl alcohol diethylene glycolether sulfate (28% aqueous solution) 10.0 g of ammonia (25% aqueoussolution) 0.7 g of 2-(2-hydroxyethyl)-4-(5-hydroxy-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-4-ylmethylene)-5-methyl-2,4- dihydropyrazol-3-one (2)1.0 g of ammonium 5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (24b) 1.1 g of2-chloro-6-ethylamino-4-nitrophenol 100.0 g water, demineralized.

The foregoing colorant solution was applied to bleached hair. After anexposure time of 20 min at 40° C., the hair was washed with water anddried. The hair color was of a medium brown shade.

Example 10 Colorant (Acidic Cream)

2.0 g of sodium lauryl sulfate 20.0 g of cetyl alcohol 5.0 g of glycerylstearate SE 2.0 g of lanolin alcohol 12.5 g of lauryl ether sulfate (28%aqueous solution) 0.3 g of ammonium5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (24b) 0.4 g of2-chloro-6-ethylamino-4-nitrophenol 0.2 g ofN-(2,3-dihydroxy)-2-nitro-4-(trifluoromethyl)aniline 100.0 g water,demineralized.

Before use, the cream was mixed with water in a 1:1 proportion andapplied to bleached hair. After an exposure time of 20 min at 40° C.,the hair was washed with a shampoo and dried. The hair color was of amedium-blond shade.

Example 11 Colorant (Combination with a Cationic Direct Dye)

10.0 g of ethanol 10.0 g of polyethylene lauryl ether (25% aqueoussolution) 0.5 g2-(2-hydroxyethyl)-4-(5-hydroxy-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-4-ylmethylene)-5-methyl-2,4-dihydropyrazol- 3-one (2) 0.2 gof di[4-diethylamino)phenyl][4-(ethylamino)naphthyl]carbenium chloride(C.I. 42595; Basic Blue No. 7) 100.0 g water, demineralized.

The foregoing colorant solution was applied to bleached hair. After anexposure of 20 min at 40° C., the hair was washed with water and dried.The hair color was of a dark-green shade.

Example 12 Colorant with Carrier

5.0 g of ethanol 2.0 g of lactic acid 2.0 g of sodium cocoamphoacetate(50% aqueous solution) 5.0 g of carrier according to the following Table1 1.2 g of ammonium 5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (24b) 0.4 g of4-amino-3-nitrophenol 100.0 g water, demineralized.

The foregoing colorant solution was applied to bleached hair. After anexposure of 20 min at 40° C., the hair was washed with water and dried.The colorant without the carrier gave a medium-blue shade, and thecolorant with the carrier gave intense blue shades.

TABLE 1 Carrier Tinting Result Comments No carrier red-brown — Washing5× strongly bluish yellow component and drying brown shade is washed out2-Hydroxymeth- saturated red-brown — ylthiophene Washing 5× saturatedred-brown no measurable color dif- and drying ference, unsensitive toshampooing

The L*a*b* color values given in the preceding examples were measuredwith a Minolta Chromameter II color-measuring instrument.

The L-value indicates the brightness (in other words, the lower the Lvalue, the higher is the color intensity). The a-value is a measure ofthe red content (namely, the higher the a-value the higher is the redcontent). The b-value is a measure of the blue content of the color, theblue content being the higher the more negative is the b-value.

The value of ΔE indicates the difference in color between the untreatedand the colored hair or between the colored and the washed hair. It isdetermined as follows:${\Delta \quad E} = \sqrt{\left( {L_{1} - L_{0}} \right)^{2} + \left( {a_{1} - a_{0}} \right)^{2} + \left( {b_{1} - b_{0}} \right)^{2}}$

where L₀, a₀ and b₀ are the values measured before coloring or beforethe washing test, and L₁, a₁ and b₁ are the values after coloring orafter the washing.

The degree of wash-out was determined according to the followingexpression:

Decolorization, %=[1−(ΔE ₂ / ΔE ₁)]×100

Here, ΔE₁ refers to the coloring step and ΔE₂ to the washing-out step.

Unless otherwise indicated, all percentages given in the presentapplication are by weight.

What is claimed is:
 1. Method for the semi-permanent tinting of hair,comprising applying to the hair a colorant composed of (a) at least onemonomethine or polymethine dye of tautomeric formula (Ia/Ib) or aphysiologically tolerated salt thereof Z=L—Z′(Ia)⇄Z′=L—Z(Ia) whereinZ=L—Z′ and Z′=L—Z are tautomers, Z and Z′ each, independently of eachother is a substitute five-membered or sex-membered heterocyclic ringand in formula (Ia) Z has a C═O— group and Z′ has a C—OH— group in saidsubstituted five-membered or six-membered heterocyclic ring whereas informula (Ib) Z has a C—OH— group and Z′ has a C═O— group in saidsubstituted five-membered or six-membered heterocyclic ring, whereineach of said substituted five-membered or six-membered heterocyclicrings is independently selected from the group consisting ofpyrazolones, pyridones, isoxazolones, dioxothiazolines, rhodanines,dioxoimidazolidines, thio barbituric acid and barbituric acid; wherein Lrepresents

wherein R is hydrogen, a phenyl group, a halogen atom, a methyl group ora carboxamido group, and wherein m and n independently of each other are0, 1 or 2, with the proviso that n+m does not exceed 2; and (b) at leastone natural or synthetic non-oxidative dye which is not a monomethine orpolymethine dye of tautomeric formula (Ia/Ib); allowing an exposure timeof 10 to 45 minutes at 20 to 50 C.; rinsing said hair with water; andthen drying said hair.
 2. The method according to claim 1, furthercomprising after said rinsing with water and before said drying, washingsaid hair with a shampoo or rinsing said hair with an aqueous solutionof a weak acid.
 3. The method according to claim 1, wherein in saidformula (Ia) and (Ib), L denotes a monomethine, trimethine orpentamethine unit.
 4. The method according to claim 1, wherein said dyeof formula (Ia) or (Ib) is selected from dyes of general formulas (II)to (IV)

wherein R1, R1′ denote hydrogen, a straight-chain or branched C1 to C8alkyl, hydroxyethyl, dihydroxypropyl, methoxyethyl, carboxyethyl or C1to C4 sulfoalkyl group, a phenyl radical, a phenyl substituted with oneor more halogen atoms, a phenyl radical substituted with one or twosulfonic acid groups, a phenyl radical substituted with one or twocarboxylic acid groups, a phenyl radical substituted with one or moreunbranched or branched C1 to C8 alkyl groups or C1 to C8 alkoxy groups,a benzyl radical, or a benzyl radical substituted with one or morehalogen atoms, a benzyl radical substituted with a C1 to C4 alkyl,hydroxyl, methoxy, carboxyl, nitro or amino group or a five-membered orsix-membered saturated or unsaturated heterocyclic ring, R1 and R1′being equal or different; R2, R2′ denote hydrogen, a branched orunbranched C1 to C6 alkyl group, a phenyl radical, an amino group whichcan also be acylated or sulfonylated, an acetyl or methoxy group or acarboxylic acid group esterified with a straight-chain or branched C1 toC8 alcohol or ethylene glycol monomethyl ether or ethylene glycolmonoethyl ether, or a carboxamido, carboxanilido or 2-amino-2-oxyethylor nitrile group, R2 and R2′ being equal or different; and R3, R3′ andR8 denotes hydrogen, a straight-chain or branched C1 to C11 alkyl group,a straight-chain or branched C1 to C11 monohydroxyalkyl group, astraight-chain or branched C1 to C11 dihydroxyalkyl group, astraight-chain or branched C1 to C11 alkoxyalkyl group, a straight-chainor branched C1 to C11 monoalkylamino group, an amino group havingformula (CH2)_(x)—NR11R12 (wherein x stands for an integer from 0 to 3and R11 and R12 independently of each other denote a C1 to C3 alkylgroup), a C2 to C4 sulfoalkyl or carboxyalkyl group, a phenyl group or aphenyl group substituted with one or more halogen atoms, or a phenylgroup substituted with one or two sulfonic acid groups, or with one ortwo carboxyl groups, or with one or more unbranched or branched C1 to C8alkyl groups or with C1 to C8 alkoxy groups, a benzyl group or a benzylgroup substituted with one or more halogen atoms, or with a C1 to C4alkyl, hydroxyl, methoxy, nitro or amino group, a phenylethyl group, afive-membered or six-membered aromatic or nonaromatic heterocyclic ringwhich can be linked directly through a methylene group, a pyrolidino,morpholino, piperazino, piperidino or pyridino (C2 or C3) alkyl group ora trialkylammonium group of formula R13—N(R14)₃ ⁺ (wherein R13 denotes aC1 to C6 alkylene group and R14 denotes a methyl or ethyl group, thetotal number of carbon atoms in the group being 5 to 9), R3 and R3′being equal or different, and R4, R4′ and R9 denotes hydrogen, anitrile, carboxylate ester, carboxamido, sulfonic acid, sulfomethyl ormethanesulfonyl group or a pyridinium or imidazolium radical, R4 and R4′being equal or different, and R5, R5′ denote hydrogen or a C1 to C4alkyl or C5-C6 cycloalkyl, phenyl, methoxyphenyl, benzyl, phenylethyl orcarboxyl group, R5 and R5′ being equal or different, and Z denotesoxygen or a radical of formula C(CN)₂, C(CN)COOQ or C(COOQ)₂ wherein Qdenotes a C1 to C8 alkyl group or an ethylene glycol mono-(C3 toC7)-alkyl ether, and L denotes a linking group of general formula

wherein R denotes a hydrogen atom, a phenyl, methyl or carboxamido groupor a halogen atom, and the indices m and n equal 0, 1 or 2, the sum of mand n not exceeding
 2. 5. The method according to claim 4, wherein thedyes of formulas (II) to (IV) are selected from the group consisting of4-(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-ylmethylene)-2,5-dimethyl-2,4-dihydropyrazol-3-one;2-(2-hydroxyethyl)-4-(5-hydroxyethyl-1-(2-hydroxyethyl)-3-methyl-1H-pyrazol-4-ylmethylene)-5-methyl-2,4-dihydropyrazol-3-one;4-(5-hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-ylmethylene)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one;diammonium4-(hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-ylmethylene)-5-methyl-2-(4-sulfophenyl)-2,4-dihyropyrazole-3-one;4-(3-(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)alkylidene-2,5-dimethyl-2,4-dihydropyrazol-3-one;5-amino-4-(3-(3-amino-5-hydroxy-1-phenyl-1H-pyrazol-4yl(allylidene)-2-phenyl-2,4-dihydropyrazol-3-one;2-(2-hydroxyethyl)-4-(3-(5-hydroxy-1(2-hydroxyethyl)-3-methyl-1H-pyrazol-4-yl)allylidene)-5methyl-2,4-dihydropyrazol-3-one;4-(3-(5-hydroxy-3-methyl-1-(4sulfophenyl)-1H-pyrazol-4yl)allylidene-5methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3one;disodium4-(3-(5-hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)allylidene)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one;4-(3-(5-hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-2-butenylidene)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3one;tripotassium4-(3-(5-hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)-2-butenylidene)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one;4-(3-(3-carboxy-5-oxo-1-(4-sulfophenyl)-1,5-dihydroxpyrazol-4-ylidene)propenyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylicacid; tetrasodium4-(3-(3-carboxy-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-ylidene)-propenyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylicacid;5-hydroxy-4-(3-(3-methoxycarbonyl-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-ylidene)-propenyl)-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylicacid methyl ester;4-(5-(5-hydroxy-1,3-dimethyl-1H-pyrazol-4-yl)penta-2,4-dienylidene)-2,5-dimethyl-2,4-dihydropyrazol-3one;5-amino-4-(5-(3-amino-5-hydroxy-1-phenyl-1H-pyrazol-4-pyrazol-4-yl)penta-2,4-dienylidene)-2-phenyl-2,4-dihydropyrazol-3-one;2-(2-hydroxyethyl)-4-(5-(5-hydroxy-1-(2-hydroxyethyl)-3methyl-1H-pyrazol-4-yl)penta-2,4-dienylidene)-5methyl-2,4-dihydropyrazol-3-one;4-(5-(5-hydroxy-3methyl)-1(4-sulfophenyl-4H-pyrazol-4-yl)penta-2,4-dienylidene)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one;dipotassium4-(5-(5-hydroxy-3-methyl-1-(4-sulfophenyl)-1H-pyrazol-4-yl)penta-2,4-dienylidene)-5-methyl-2-(4-sulfophenyl)-2,4-dihydropyrazol-3-one;4-(5-(3-carboxy-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-ylidene)penta-1,3-dienyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylicacid; dipotassium4-(5-(3-carboxy-5oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-ylidene)penta-1,3-dienyl)-5-hydroxy-1-(4-sulfophenyl)-1H-pyrazol-3-carboxylicacid;6-hydroxy-1-(2-hydroxyethyl)-5-(3-(1-(2-hydroxyethyl)-3-methyl-5-oxo-1,5-dihydropyrazol-4-ylidene)propenyl)-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile;6-hydroxy-5-(3-(1-(2-hydroxyethyl)-3-methyl-5-oxo-1,5-dihydropyrazol-4-ylidene)propenyl)-4-methyl-2-oxo-1-(4-sulfophenyl)-1,2-dihydropyridine-3-carbonitrile;6-hydroxy-4-methyl-5-(3-(3-methyl-5-oxo-1-(4-sulfophenyl)-1,5-dihydropyrazol-4-ylidene)propenyl)-2-oxo-1-(4sulfophenyl)-1,2-dihydropyridine-3-carbonitrile;6-hydroxy-4-methyl-5-(3-(3-methyl-5-oxo-1-phenyl-1,5-dihydropyrazol-4-ylidene)propenyl)-2-oxo-1-(3-sulfophenyl)-1,2-dihydropyridine-3-carbonitrile;4-(3-(5-cyano-2-hydroxy-4-methyl-6-oxo-1-phenyl-1,6-dihydropyridin-3-yl)allylidene)-5-oxo-1-(4-sulfophenyl)-4,5-dihydro-1H-pyrazole-3-carboxylicacid;6-hydroxy-5-(3-(1-(2-hydroxyethyl)-3-methyl-5-oxo-1,5-dihydropyrazol-4-ylidene)propenyl)-4-methyl-2-oxo-1-phenyl-1,2-dihydropyridine-3-carbonitrile;5-(3-(4-carboxy-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-6-hydroxy-2oxo-1,2-dihydropyridine-4-carboxylicacid;2-(3-cyano-5-(3-(5-cyano-6-dicyanomethylene-4-methyl-2-oxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-6-hydroxy-4-methyl-1H-pyridin-2-ylidene)malononitrile;5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2dihydropyridine-3-carbonitrile;triethylammonium5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile;5-(3-(5-cyano-1-(2-hydroxyethyl)-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-6-hydroxy-1-(2-hydroxyethyl)-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile;5-(3-(5-cyano-1-ethyl-4-(4-methoxyphenyl)-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-1-ethyl-6-hydroxy-4-(4-methoxyphenyl)-2-oxo-1,2-dihydropyridine-3-carbonitrile;1-butyl-5-(3-(1-butyl-5-cyano-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile;5-(3-(5-cyano-1-(3-methoxypropyl)-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-1-ethyl-6-hydroxy-1-(3-methoxypropyl)-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile;5-(3-(5-cyano-1-cyclohexyl-4-methyl-2,6-dioxo-1,6dihydro-2H-pyridin-3-ylidene)-propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile;5-(3-(5-cyano-4-methyl-1-(2-morpholin-4-ylethyl)-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-6-hydroxy-4-methyl-1-(2-morpholin-4-ylethyl)-2-oxo-1,2-dihydropyridine-3-carbonitrile;5-(3-(5-cyano-4-methyl-2,6-dioxo-1-(4-sulfophenyl-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-6-hydroxy-4-methyl-2-oxo-1-(4-sulfophenyl)-1,2-dihydropyridine-3-carbonitrile;5-(3-(5-cyano-4-methyl-2,6-dioxo-1-(3-sulfophenyl)-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-6-hydroxy-4-methyl-2-oxo-1-(3-sulfophenyl)-1,2-dihydropyridine-3-carbonitrile;5-(3-(5-cyano-1-dimethylamino-4-methyl-2,6-dioxo-1,6dihydro-2H-pyridin-3-ylidene)propenyl)-1-dimethylamino-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile;5-(3-(5-carbamoyl-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carboxamide;1-ethyl-3-(3-(1-ethyl-2-hydroxy-5-methanesulfonyl-4-methyl-6-oxo-1,6-dihydropyridin-3-yl)allylidene)-5-methanesulfonyl-4-methyl-3H-pyridine-2,6-dione;5-(5-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)penta-1,3-dienyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrileand ammonium5-(3-(5-cyano-1-ethyl-4-methyl-2,6-dioxo-1,6-dihydro-2H-pyridin-3-ylidene)propenyl)-1-ethyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile.6. The method according to claim 1, wherein said physiologicallytolerated salt is selected from the group consisting of the ammonium,sodium, potassium, triethylammonium, N-methylmorpholinium,monoethanolammonium, diethanolammonium and triethanolammonium salts. 7.The method according to claim 1, wherein said colorant has a pH value offrom 2 to
 11. 8. The method according to claim 1, wherein said colorantcontains from 0.01 to 5% by weight of said dye of formula (Ia/Ib). 9.The method according to claim 1, wherein said colorant contains from0.01 to 15% by weight of said non-oxidative dye.
 10. The methodaccording to claim 1, wherein said non-oxidative dye is selected fromthe group consisting of natural dyes, nitro dyes, azo dyes, quinonedyes, triphenylmethane dyes and basic or acid dyes.